CN107316927B - Core-shell structure white light emitting device and preparation method thereof - Google Patents
Core-shell structure white light emitting device and preparation method thereof Download PDFInfo
- Publication number
- CN107316927B CN107316927B CN201710706337.8A CN201710706337A CN107316927B CN 107316927 B CN107316927 B CN 107316927B CN 201710706337 A CN201710706337 A CN 201710706337A CN 107316927 B CN107316927 B CN 107316927B
- Authority
- CN
- China
- Prior art keywords
- zno
- zns
- shell
- film
- core
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011258 core-shell material Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002073 nanorod Substances 0.000 claims abstract description 137
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000010408 film Substances 0.000 claims description 156
- 238000000151 deposition Methods 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 45
- 239000010409 thin film Substances 0.000 claims description 20
- 230000008021 deposition Effects 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 238000005566 electron beam evaporation Methods 0.000 claims description 17
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 17
- 230000005284 excitation Effects 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 12
- 238000004020 luminiscence type Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000004070 electrodeposition Methods 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 238000000295 emission spectrum Methods 0.000 claims description 3
- 229910052594 sapphire Inorganic materials 0.000 claims description 3
- 239000010980 sapphire Substances 0.000 claims description 3
- 230000010354 integration Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 134
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 13
- 229910052786 argon Inorganic materials 0.000 description 12
- 239000000919 ceramic Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 6
- VZPPHXVFMVZRTE-UHFFFAOYSA-N [Kr]F Chemical compound [Kr]F VZPPHXVFMVZRTE-UHFFFAOYSA-N 0.000 description 5
- 238000000137 annealing Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- 238000003491 array Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000007888 film coating Substances 0.000 description 3
- 238000009501 film coating Methods 0.000 description 3
- 239000004312 hexamethylene tetramine Substances 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 238000005086 pumping Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/08—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a plurality of light emitting regions, e.g. laterally discontinuous light emitting layer or photoluminescent region integrated within the semiconductor body
Abstract
The application relates to the technical field of photoelectric integration, in particular to a white light emitting device with a core-shell structure and a preparation method thereof, and is characterized in that a GaN substrate layer is arranged on the bottom substrate of the white light emitting device, a ZnO film seed layer is arranged above the GaN substrate layer, a ZnO nano rod is arranged above the ZnO film seed layer, a ZnS-Mn film shell layer is coated around the ZnO nano rod, the ZnO nano rod and the ZnS-Mn film shell layer form a ZnO/ZnS-Mn core-shell nano rod array, the ZnS-Mn film shell layer, the ZnO nano rod, the ZnO film seed layer and the GaN substrate layer form a ZnS-Mn/ZnO/GaN core-shell nano rod array device, and blue light emitted by the GaN substrate layer can penetrate through the upper material and be overlapped with yellow-green light of the ZnO nano rod and orange-red light of the ZnS-Mn film shell layer to obtain white light.
Description
Technical Field
The application relates to the technical field of photoelectric integration, in particular to a core-shell structure white light emitting device which has the advantages of simple structure, no need of fluorescent powder, no pollution, low cost, high and stable luminous efficiency and a preparation method thereof.
Background
The white light LED is a novel semiconductor cold light source for directly converting electric energy into white light, has the advantages of high efficiency, no pollution, long service life, quick response, small volume, easy maintenance and the like, is called a fourth-generation illumination light source (or a green illumination light source), and has wide application prospect in the fields of illumination, display and military.
At present, three schemes for realizing a white light LED are mainly adopted, namely, a blue light LED is utilized to excite yellow fluorescent powder, and an ultraviolet light LED is utilized to excite red, green and blue three primary color fluorescent powder. At present, the commercialized white light LED adopts two schemes, however, both approaches comprise a secondary excitation process, so that the luminous efficiency of the device is reduced, and the further development of the device is restricted to a certain extent; the third scheme is to package the red, green and blue LEDs together to obtain white light directly, but because the driving voltages of the three LEDs are different, the control circuit of the device is more complex, and the energy consumption is greatly improved. In view of the above problems, it is always desired to realize a single chip semiconductor white light emitting device without fluorescent powder, and particularly in the actual production process, the qualification rate of the product is generally checked after the complete light emitting device is manufactured, that is, the electrode is installed, and the unqualified product is destroyed, so that the working difficulty is increased, and particularly, the production cost is increased in the process of increasing the electrode.
Disclosure of Invention
The application aims to solve the defects of the prior art and provide a core-shell structure white light emitting device which has the advantages of simple structure, no need of fluorescent powder, no pollution, low cost, high and stable luminous efficiency and a preparation method thereof.
The technical scheme adopted for solving the technical problems is as follows:
a white light emitting device with a core-shell structure is characterized in that a bottom substrate of the white light emitting device is a GaN substrate layer, a ZnO film seed layer is arranged above the GaN substrate layer, a ZnO nano rod is arranged above the ZnO film seed layer, a ZnS: mn film shell layer is wrapped around the ZnO nano rod, the ZnO nano rod and the ZnS: mn film shell layer form a ZnO/ZnS: mn core-shell nano rod array, the ZnS: mn film shell layer, the ZnO nano rod, the ZnO film seed layer and the GaN substrate layer form a ZnS: mn/ZnO/GaN core-shell nano rod array device, and blue light emitted by the GaN substrate layer can penetrate through an upper material under the excitation of ultraviolet light with the wavelength of 325nm, and can be overlapped with yellow-green light of the ZnO nano rod and orange-red light of the ZnS: mn film shell layer to obtain white light.
The ZnO/ZnS-Mn core-shell nanorod array is characterized in that transparent conductive films are filled in array gaps and tops of the ZnO/ZnS-Mn core-shell nanorod arrays, the gaps among the ZnO/ZnS-Mn core-shell nanorod arrays are filled by the transparent conductive films, the ZnO/ZnS-Mn core-shell nanorod arrays are connected through the transparent conductive films, pt/Ni (50 nm/30 nm) electrodes are arranged on the surface of a GaN substrate layer, pt/Ti (50 nm/30 nm) electrodes are arranged on the surface of a ZnS-Mn/ZnO core-shell layer with the transparent conductive films, and the device shows white light emission under forward voltage excitation.
The preparation method of the core-shell structure white light emitting device is characterized by comprising the following steps of:
step one: cleaning a GaN substrate, namely, an Mg-doped p-GaN epitaxial wafer (taking sapphire (0001) as the substrate, growing an Mg-doped p-GaN film with the thickness of about 1 mu m on an undoped GaN buffer layer), sequentially placing the GaN substrate into acetone and ethanol solution, ultrasonically oscillating and cleaning for 10-30min, then washing with deionized water, drying with nitrogen, and enabling the luminescence peak position of the GaN substrate layer to be 430-450nm;
step two: depositing a ZnO film seed layer on the GaN substrate layer, wherein the method for depositing the ZnO film seed layer comprises the following steps: the thickness of the deposited ZnO is 30-50nm by a pulse laser deposition method, a magnetron sputtering method and an electron beam evaporation method;
step three: the ZnO nano rod is prepared on the ZnO film seed layer, and the method for preparing the ZnO nano rod comprises the following steps: hydrothermal synthesis, chemical water bath deposition and electrodeposition, wherein the luminescence peak positions of the ZnO nano rod are 375-387nm and 560-580nm;
step four: the ZnO nano rod is coated with a ZnS:Mn film shell layer, and the method for depositing the ZnS:Mn film shell layer comprises the following steps: pulse laser deposition, magnetron sputtering and electron beam evaporation, wherein the luminescence peak position of a ZnS: mn film shell layer is 580-610nm, a ZnO nano rod and a ZnS: mn film shell layer form a ZnO/ZnS: mn core-shell nano rod array, a ZnS: mn film shell layer, a ZnO nano rod, a ZnO film seed layer and a GaN substrate layer form a ZnS: mn/ZnO/GaN core-shell nano rod array device, blue light emitted by the GaN substrate layer can penetrate through an upper surface material under the excitation of ultraviolet light with 325nm wavelength, and the blue light and yellow-green light of the ZnO nano rod and orange-red light of the ZnS: mn film shell layer are overlapped to obtain white light, and the color coordinates are (0.31-0.35, 0.30-0.34) and then an electrode is added for practical production;
step five: depositing a transparent conductive film with the thickness of 100-120nm on the top end of the ZnO/ZnS-Mn core-shell nano-rod array, filling the transparent conductive film in a gap of the ZnO/ZnS-Mn core-shell nano-rod array, and covering the top end of the ZnO/ZnS-Mn core-shell nano-rod array to enable the ZnO/ZnS-Mn core-shell nano-rod array to be connected with each other;
step six: preparing Pt/Ni (50 nm/30 nm) electrodes on the GaN substrate layer respectively, and preparing Pt/Ti (50 nm/30 nm) electrodes on the transparent conductive film coated with ZnO/ZnS: mn core-shell nanorod array surface;
step seven: the ZnS: mn/ZnO/GaN core-shell nanorod array is excited by forward voltage to obtain white light emission with stronger visible light region, the wavelength range of the obtained white light emission spectrum is 350-800nm, and the color coordinates are (0.335-0.3393, 0.3334-0.3366).
The transparent conductive film is an ITO transparent conductive film, and the ITO transparent conductive film at the uppermost layer does not influence luminous efficiency and is simple and convenient to manufacture.
According to the ZnS: mn thin film shell layer, the doping concentration of Mn < 2+ > is 1% -3%, and orange red light emission with proper intensity of about 580-610nm of Mn < 2+ > can occur in the ZnS: mn thin film shell layer under the doping concentration, so that a core-shell nanorod array device can generate good luminous color coordinates.
According to the ZnS: mn thin film shell layer, the optimal doping concentration of Mn & lt2+ & gt is 1%, and orange red light emission with proper intensity of about 580-610nm of Mn & lt2+ & gt can occur in the ZnS: mn thin film shell layer under the doping concentration, so that the core-shell nanorod array device can generate optimal luminous color coordinates.
By adopting the structure and the preparation method, the application has the advantages of simple structure, no need of fluorescent powder, no pollution, low cost, high and stable luminous efficiency, and the like.
Drawings
Fig. 1 is a schematic structural view of the present application.
Fig. 2 is a schematic view of a structure with electrodes.
Fig. 3 is a schematic structural view of the transparent conductive film.
Fig. 4 is a chromaticity diagram of the present application.
Detailed Description
The application is further described below with reference to the accompanying drawings:
as shown in the attached drawings, the white light emitting device with the core-shell structure is characterized in that a bottom substrate of the white light emitting device is a GaN substrate layer 1, a ZnO film seed layer 2 is arranged above the GaN substrate layer 1, a ZnO nano rod 3 is arranged above the ZnO film seed layer 2, and ZnS is coated around the ZnO nano rod 3: mn thin film shell layer 4, znO nano rod 3 and ZnS: mn thin film shell layer 4 form a ZnO/ZnS: mn core-shell nano rod array, znS: mn thin film shell layer 4, znO nano rod 3, znO thin film seed layer 2 and GaN substrate 1 form a ZnS: mn/ZnO/GaN core-shell nano rod array device, the ZnS: mn/ZnO/GaN core-shell nano rod array device is excited by ultraviolet light with 325nm wavelength, blue light emitted by GaN substrate layer 1 can penetrate through the upper surface material and be overlapped with yellow green light of ZnO nano rod 3 and orange red light of ZnS: mn thin film shell layer 4 to obtain white light, the array gap of the ZnO/ZnS: mn core-shell nano rod array and the gap between the top of the ZnO/ZnS: mn core-shell nano rod array are filled with transparent conductive films 5, the ZnO/ZnS: mn core-shell nano rod array is mutually connected through the transparent conductive films 5, pt/Ni (50 nm/30 nm) electrodes 6 are arranged on the surface of GaN substrate layer 1, and the surface of ZnS: mn core-shell layer with the transparent conductive films is provided with Pt/Ni (50 nm/30 nm) electrodes are excited at a positive voltage of the Ti/30 nm, and the white light is excited by the electrodes.
The preparation method of the core-shell structure white light emitting device is characterized by comprising the following steps of:
step one: cleaning a GaN substrate, namely, an Mg-doped p-GaN epitaxial wafer (taking sapphire (0001) as the substrate, growing an Mg-doped p-GaN film with the thickness of about 1 mu m on an undoped GaN buffer layer), sequentially placing the GaN substrate into acetone and ethanol solution, ultrasonically oscillating and cleaning for 10-30min, then washing with deionized water, drying with nitrogen, and enabling the luminescence peak position of the GaN substrate layer to be 430-450nm;
step two: depositing a ZnO film seed layer on the GaN substrate layer, wherein the method for depositing the ZnO film seed layer comprises the following steps: the thickness of the deposited ZnO is 30-50nm by a pulse laser deposition method, a magnetron sputtering method and an electron beam evaporation method;
step three: the ZnO nano rod is prepared on the ZnO film seed layer, and the method for preparing the ZnO nano rod comprises the following steps: hydrothermal synthesis, chemical water bath deposition and electrodeposition, wherein the luminescence peak positions of the ZnO nano rod are 375-387nm and 560-580nm;
step four: the ZnO nano rod is coated with a ZnS:Mn film shell layer, and the method for depositing the ZnS:Mn film shell layer comprises the following steps: pulse laser deposition, magnetron sputtering and electron beam evaporation, wherein the luminescence peak position of a ZnS: mn film shell layer is 580-610nm, a ZnO nano rod and a ZnS: mn film shell layer form a ZnO/ZnS: mn core-shell nano rod array, a ZnS: mn film shell layer, a ZnO nano rod, a ZnO film seed layer and a GaN substrate layer form a ZnS: mn/ZnO/GaN core-shell nano rod array device, blue light emitted by the GaN substrate layer can penetrate through an upper surface material under the excitation of ultraviolet light with 325nm wavelength, and the blue light and yellow-green light of the ZnO nano rod and orange-red light of the ZnS: mn film shell layer are overlapped to obtain white light, and the color coordinates are (0.31-0.35, 0.30-0.34) and then an electrode is added for practical production;
step five: depositing a transparent conductive film with the thickness of 100-120nm on the top end of the ZnO/ZnS-Mn core-shell nano-rod array, filling the transparent conductive film in a gap of the ZnO/ZnS-Mn core-shell nano-rod array, and covering the top end of the ZnO/ZnS-Mn core-shell nano-rod array to enable the ZnO/ZnS-Mn core-shell nano-rod array to be connected with each other;
step six: preparing Pt/Ni (50 nm/30 nm) electrodes on the GaN substrate layer respectively, and preparing Pt/Ti (50 nm/30 nm) electrodes on the transparent conductive film coated with ZnO/ZnS: mn core-shell nanorod array surface;
step seven: the ZnS: mn/ZnO/GaN core-shell nanorod array is excited by forward voltage to obtain white light emission with stronger visible light region, the wavelength range of the obtained white light emission spectrum is 350-800nm, and the color coordinates are (0.335-0.3393, 0.3334-0.3366).
The transparent conductive film is an ITO transparent conductive film, and the ITO transparent conductive film at the uppermost layer does not influence luminous efficiency and is simple and convenient to manufacture.
According to the ZnS: mn thin film shell layer, the doping concentration of Mn < 2+ > is 1% -3%, and orange red light emission with proper intensity of about 580-610nm of Mn < 2+ > can occur in the ZnS: mn thin film shell layer under the doping concentration, so that a core-shell nanorod array device can generate good luminous color coordinates.
According to the ZnS: mn thin film shell layer, the optimal doping concentration of Mn & lt2+ & gt is 1%, and orange red light emission with proper intensity of about 580-610nm of Mn & lt2+ & gt can occur in the ZnS: mn thin film shell layer under the doping concentration, so that the core-shell nanorod array device can generate optimal luminous color coordinates.
In the fifth step, the transparent conductive film can be replaced by another transparent conductive film with cost saving, and the manufacturing steps are as follows:
step 1: depositing a ZnO film layer on the top end of the ZnO/ZnS:Mn core-shell nanorod array, wherein the method for depositing the ZnO film layer comprises the following steps: the thickness of the deposited ZnO is 20-60nm by a pulse laser deposition method, an electron beam evaporation method and a magnetron sputtering method;
step 2: an Au film layer is deposited on the ZnO film, and the method for depositing the Au film layer comprises the following steps: pulsed laser deposition, electron beam evaporation, and magnetron sputtering. The thickness of the Au layer is 6-30nm;
step 3: depositing a ZnS thin film layer on the Au film, wherein the method for depositing the ZnS thin film layer comprises the following steps: the thickness of ZnS deposited by pulse laser deposition, electron beam evaporation and magnetron sputtering is 20-60nm.
The application has the following advantages and beneficial effects:
the core-shell structure white light emitting device has the advantages that:
1. the device has simple structure, no need of fluorescent powder, no pollution, low cost, high and stable luminous efficiency.
2. The ZnS: mn/ZnO/GaN core-shell nanorod array system is adopted, so that the light absorption efficiency is enhanced, the optical characteristics are excellent, and the electron transporting capability is also high.
The ZnS: mn layer coated on the outside of the ZnO nano rod can enable the color coordinates of the luminescent light of the device to be closer to that of standard white light (0.33 ).
4. The ITO transparent conductive film at the uppermost layer does not influence the luminous efficiency, and the manufacture of the device is simplified.
5. The minimum turn-on voltage of the device is about 6V, which is significantly less than the turn-on voltage of the device reported in the literature.
6. Better white light emission can be obtained whether ultraviolet light excitation or voltage excitation is used.
7. The production cost is reduced, and the working efficiency is quickened.
8. The GaN substrate layer is provided with a ZnO film seed layer which is used as a buffer layer and a nucleation seed layer for the growth of ZnO nano rods, and the function of the ZnO film seed layer can reduce lattice mismatch between the ZnO nano rods and the substrate, so that the ZnO nano rods uniformly and vertically grow in order, and due to the existence of the ZnO film seed layer, the ZnO nano rods obtained by growth are orderly arranged, compact in structure and better in directivity, and the luminescent performance of the ZnS: mn/ZnO/GaN core-shell nano rod array is good.
9. The Mn & lt2+ & gt doping concentration in the ZnS: mn film shell layer is 1.0%, and orange red light emission of about 580-610nm of Mn & lt2+ & gt appears in the obtained ZnS: mn film shell layer according to the preparation method and the preparation conditions, so that the core-shell nanorod array device can generate optimized luminous color coordinates.
Under the condition that other factors of the preparation method and the preparation conditions of the product are the same, the electroluminescent peak position and the luminescent color coordinate are obtained according to the difference of Mn & lt2+ & gt doping concentration in a ZnS: mn film shell layer, and the table is as follows (Table one):
table one:
as can be seen from table one: under the condition that the doping concentration of Mn & lt2+ & gt is 1% -3%, the electroluminescent long wavelength peak position is about 600nm, and the electroluminescent long wavelength peak position is due to the fact that orange red light emission of about 600nm of Mn & lt2+ & gt occurs in a ZnS: mn film shell layer of a product, wherein when the doping concentration is 1.0%, the luminous color coordinates of the core-shell nanorod array device are closest to standard white light (0.33 ).
Under the condition that other factors such as the preparation method and the preparation conditions of the product are all the same, different luminous color coordinate tables generated according to different excitation voltages are as follows (Table two):
and (II) table:
from Table two, it can be seen that: under the condition of excitation voltage of 6-20V with lower excitation voltage, the LED lamp can generate luminous color coordinates close to standard white light (0.33 ), and under high-voltage excitation, high heat can be generated due to high voltage, so that the LED lamp is easy to damage, the service life of the LED lamp is reduced, and the LED lamp meets the green energy production standard.
The transparent conductive film has the advantages that:
in the original ITO transparent conductive film, the ITO transparent conductive film contains In element, but the In content In the nature is extremely small, the price is high, and the single-layer transparent conductive oxide film is easy to oxidize at high temperature and difficult to realize stable doping; high transmittance (> 86.6%), low sheet resistance (< 26 Ω/sq), high quality factor (> 6.562 ×10-3 Ω -1); the heat stability and the corrosion resistance are strong; znO is used as a bottom layer medium, znS is used as a surface layer medium, oxidation of a metal Au layer in the preparation process can be effectively prevented, and the photoelectric property of the transparent conductive three-layer composite film is improved.
Embodiments of a core-shell structured light emitting device in the present application:
example 1
Step one: cleaning a GaN substrate, sequentially putting the GaN substrate into acetone and ethanol solution, carrying out ultrasonic oscillation cleaning for 10-30min, then washing the GaN substrate with deionized water, and drying the GaN substrate with nitrogen;
step two: depositing a ZnO film seed layer on the GaN substrate layer by using an electron beam evaporation method, wherein the purity of a ZnO target is 99.99%, the vacuum degree is better than 1.0x10 < -4 > Pa, the electron beam current is 8 mA during film coating, the anode voltage is 6 kV, the evaporation time is 10-20 min, the substrate temperature is RT-300 ℃, and the thickness of the ZnO film is 30-50nm;
step three: preparing ZnO nano-rods on a ZnO film seed layer by an electrodeposition method, accurately weighing a certain amount of Zn (NO 3) 2 6H 2O, dissolving in deionized water, and preparing an electrodeposition solution with a certain concentration; the temperature of the electrodeposition solution is controlled to be 60-80 ℃, the electrodeposition time is controlled to be 1-2 h, 2.0 cm multiplied by 2.5 cm conductive glass is used as a working electrode, a Pt electrode is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and a constant potential method is adopted to prepare the ZnO nanorod array.
Step four: coating a ZnS-Mn film layer on a ZnO nano-rod by using an electron beam evaporation method, wherein the purity of a ZnS-Mn target is 99.99%, the vacuum degree is better than 1.0x10 < -4 > Pa, the electron beam is 8 mA during coating, the anode voltage is 6 kV, the evaporation time is 20-40 min, the substrate temperature is 200-300 ℃, after evaporation, the ZnS-Mn film sample is annealed for 0.5-1h at 300-400 ℃ under the vacuum condition of 7.5x10 < -5 > Pa, the luminous peak position of the ZnS-Mn film is 580-610nm, the ZnO nano-rod and the ZnS-Mn film shell form a ZnO/ZnS core-shell nano-rod array, the ZnS-Mn film shell, the ZnO nano-rod, the ZnO film seed layer and the GaN substrate layer form a ZnS-Mn/ZnO/GaN core-shell nano-rod array device, and blue light emitted by the GaN substrate layer can penetrate through an upper surface material under the excitation of ultraviolet light with the wavelength of the ZnO nano-rod, and orange red light of the ZnS-Mn film shell layer are overlapped together, and then the white light is produced, and practical production is carried out;
step five: and depositing an ITO transparent conductive film with the thickness of 100-120nm on the top end of the ZnO/ZnS-Mn core-shell nano-rod array by using an electron beam evaporation method, filling the transparent conductive film in a gap of the ZnO/ZnS-Mn core-shell nano-rod array, and covering the top end of the ZnO/ZnS-Mn core-shell nano-rod array to enable the ZnO/ZnS-Mn core-shell nano-rod array to be connected with each other.
Step six: preparing Pt/Ni (50 nm/30 nm) electrodes on the surface of the GaN substrate layer by an electron beam evaporation method, preparing Pt/Ti (50 nm/30 nm) electrodes on a transparent conductive film coated with ZnO/ZnS and Mn core-shell nanorod array surface by an electron beam evaporation method, and annealing a sample at 300-500 ℃ for 10-30min in order to ensure better ohmic contact;
step seven: exciting ZnS: mn/ZnO/GaN core-shell nanorod array by using forward voltage of 6-20V to obtain white light with wavelength of 350-900nm in visible light region.
Example 2
Step one: cleaning a GaN substrate, sequentially putting the GaN substrate into acetone and ethanol solution, carrying out ultrasonic oscillation cleaning for 10-30min, then washing the GaN substrate with deionized water, and drying the GaN substrate with nitrogen;
step two: depositing a ZnO film seed layer on a GaN substrate layer by using a pulse laser deposition method, focusing on a ZnO ceramic target (99.99%) by using a krypton fluoride excimer laser with wavelength of 248 nm and pulse width of 10 ns, wherein the laser pulse energy is 250-350 mJ, the laser pulse repetition frequency is 5-10Hz, the focusing area on the ceramic target is 4 mm <2 >, the energy density is 6J/cm <2 >, the back vacuum of a vacuum chamber is 10-7 Pa, the source-base distance during ZnO deposition is 4-6 cm, the growth temperature is RT-300 ℃, and the thickness of a ZnO film is 30-50nm;
step three: preparing ZnO nano rods on a ZnO film seed layer by a hydrothermal synthesis method, respectively preparing a Zn (NO 3) 2 solution and a Hexamethylenetetramine (HMT) solution with the concentration of 0.01-0.03 mol/L, mixing the solutions with the molar ratio of 1:1, pouring the mixed solution into a hydrothermal reaction kettle, then placing the prepared GaN substrate into the reaction kettle, placing the reaction kettle into an electric constant-temperature blast drying box, heating the reaction kettle to 90-120 ℃ for 2-5 hours, naturally cooling the reaction kettle to room temperature after the reaction is finished, taking out a sample, flushing the sample with a large amount of deionized water, and then placing the sample into an oven to dry the sample at 80-100 ℃ for 0.5-1 hour, wherein the luminous peak positions of the ZnO nano rods are 373-387nm and 560-580nm;
step four: a ZnS: mn film layer is coated on a ZnO nano rod by a pulse laser deposition method, a krypton fluoride excimer laser with the wavelength of 248 nm and the pulse width of 10 ns is used, the excimer laser is focused on a ZnS: mn ceramic target (99.99%), the laser pulse energy is 250-350 mJ, the laser pulse repetition frequency is 5Hz, the area focused on the ceramic target is 4 mm <2 >, and the energy density is 6J/cm <2 >. The back vacuum of the vacuum chamber is 10 < -7 > Pa, the source-base distance of ZnS: mn deposition is 4-6 cm, the growth temperature is 200-300 ℃, the luminous peak position of a ZnS: mn film is 580-610nm, a ZnO nano rod and a ZnS: mn film shell form a ZnO/ZnS: mn core-shell nano rod array, a ZnS: mn film shell, a ZnO nano rod, a ZnO film seed layer and a GaN substrate layer form a ZnS: mn/ZnO/GaN core-shell nano rod array device, under the excitation of ultraviolet light with the wavelength of 325nm, blue light emitted by the ZnS: mn/ZnO/GaN core-shell nano rod array device can penetrate through the upper material and be overlapped with yellow-green light of the ZnO nano rod and orange-red light of the ZnS: mn film shell to obtain white light, and then the electrode is increased for practical production;
step five: and depositing an ITO transparent conductive film with the thickness of 100-120nm on the top end of the ZnO/ZnS-Mn core-shell nano-rod array by using a pulse laser deposition method, filling the transparent conductive film in a gap of the ZnO/ZnS-Mn core-shell nano-rod array, and covering the top end of the ZnO/ZnS-Mn core-shell nano-rod array to enable the ZnO/ZnS-Mn core-shell nano-rod array to be connected with each other.
Step six: preparing Pt/Ni (50 nm/30 nm) electrodes on the surface of the GaN substrate layer by a pulse laser deposition method, preparing Pt/Ti (50 nm/30 nm) electrodes on a transparent conductive film coated with ZnO/ZnS: mn core-shell nanorod array surface by a pulse laser deposition method, and annealing the sample at 300-500 ℃ for 10-30min in order to ensure better ohmic contact;
step seven: exciting ZnS: mn/ZnO/GaN core-shell nanorod array by using forward voltage of 6-20V to obtain white light with wavelength of 350-900nm in visible light region.
Example 3
Step one: cleaning a GaN substrate, sequentially placing the GaN substrate into acetone and ethanol solution, carrying out ultrasonic oscillation cleaning for 10-30min, then washing the GaN substrate with deionized water, and drying the GaN substrate with nitrogen.
Step two: depositing a ZnO film seed layer on a GaN substrate layer by using a magnetron sputtering method, wherein the purity of a ZnO target is 99.99%, the background vacuum is 6 multiplied by 10 < -4 > Pa, 99.9% high-purity argon is adopted, the argon pressure is 0.1-0.3Pa, the argon flow is 20sccm, the sputtering power is 100W, the distance between the target and the substrate is 4-6 cm, the deposition temperature is RT-300 ℃, the deposition time is 0.5-1h, and the thickness of a ZnO film is 30-50nm;
step three: preparing ZnO nano-rods on a ZnO film seed layer by a chemical water bath deposition method, preparing an aqueous solution of zinc nitrate (taking the zinc nitrate as a Zn source) and hexamethylenetetramine (C6H 12N 4) in a certain proportion, wherein the mass ratio of Zn (NO 3) 2 to C6H12N4 is 1:1, vertically placing a GaN substrate layer with the ZnO film seed layer in the solution, standing for 2-4H at a certain water bath temperature (20-90 ℃), taking out a sample from the solution, rinsing with deionized water to remove sediment attached to the surface, and then putting the solution into an oven to dry for 0.5-1H at 60-80 ℃, wherein the luminous peak positions of the ZnO nano-rods are 373-387nm and 560-580nm.
Step four: coating ZnS: mn film layer on ZnO nano rod by magnetron sputtering method, pumping back vacuum to 10-4Pa by using a mechanical pump and molecular pump two-stage vacuum pumping system, introducing high purity 20sccm Ar gas, vacuum maintaining sputtering chamber at 2.0-3.0Pa, maintaining substrate temperature at 200-300 deg.C, and adjusting radio frequency to 120W. The deposition time is 0.5-1h, and the luminescence peak position of the ZnS: mn film is 595nm; the ZnO nanorods and ZnS: mn thin film shells form a ZnO/ZnS: mn core-shell nanorod array, the ZnS: mn thin film shells, the ZnO nanorods, the ZnO thin film seed layer and the GaN substrate layer form a ZnS: mn/ZnO/GaN core-shell nanorod array device, blue light emitted by the GaN substrate layer can penetrate through the upper surface material under the excitation of ultraviolet light with the wavelength of 325nm, and the blue light and yellow-green light of the ZnO nanorods and orange-red light of the ZnS: mn thin film shells are overlapped together to obtain white light, and then the electrode is added for production practicality;
step five: and depositing an ITO transparent conductive film with the thickness of 100-120nm on the top end of the ZnO/ZnS-Mn core-shell nano-rod array by using a magnetron sputtering method, filling the transparent conductive film in a gap of the ZnO/ZnS-Mn core-shell nano-rod array, and covering the top end of the ZnO/ZnS-Mn core-shell nano-rod array to enable the ZnO/ZnS-Mn core-shell nano-rod array to be connected with each other.
Step six: and preparing Pt/Ni (50 nm/30 nm) electrodes on the surface of the GaN substrate layer by a magnetron sputtering method, preparing Pt/Ti (50 nm/30 nm) electrodes on a transparent conductive film coated with ZnO/ZnS: mn core-shell nanorod array surface by the magnetron sputtering method, and annealing the sample at 300-500 ℃ for 10-30min in order to ensure better ohmic contact.
Step seven: exciting ZnS: mn/ZnO/GaN core-shell nanorod array by using forward voltage of 6-20V to obtain white light with wavelength of 350-900nm in visible light region.
Embodiments of transparent conductive film in core-shell structured light emitting devices of the present application
Example 1
Step 1: depositing a ZnO film layer on the top end of the Mn core-shell nanorod array by using a pulse laser deposition method, focusing on a ZnO ceramic target (99.99%) by using a krypton fluoride excimer laser with wavelength of 248 nm and pulse width of 10 ns, wherein the laser pulse energy is 250-300 mJ, the laser pulse repetition frequency is 5-10Hz, the area focused on the ceramic target is 4 mm <2 >, the energy density is 6J/cm <2 >, the back vacuum of a vacuum chamber is 10-7 Pa, the source-base distance during ZnO deposition is 4-6 cm, the growth temperature is room temperature RT-300 ℃, and the thickness of the ZnO film is 20-60nm;
step 2: depositing an Au film layer on the ZnO film layer by using a pulse laser deposition method, focusing on an Au target (99.999%) by using a krypton fluoride excimer laser with the wavelength of 248 nm and the pulse width of 10 ns, wherein the laser pulse energy is 300-350 mJ, the laser pulse repetition frequency is 5-10Hz, the focusing area on the ceramic target is 4 mm <2 >, and the energy density is 6J/cm <2 >. The back vacuum of the vacuum chamber is 10 < -7 > Pa, the source-base distance during Au deposition is 4-6 cm, and the growth temperature is room temperature RT-100 ℃. The thickness of the Au film is 6-30nm.
Step 3: depositing a ZnS film layer on the Au film layer by using a pulse laser deposition method, focusing on a ZnS ceramic target (99.99%) by using a krypton fluoride excimer laser with wavelength of 248 nm and pulse width of 10 ns, wherein the laser pulse energy is 250-350 mJ, the laser pulse repetition frequency is 5-10Hz, the focusing area on the ceramic target is 4 mm <2 >, and the energy density is 6J/cm <2 >. The back vacuum of the vacuum chamber is 10-7 Pa, the source-base distance during ZnS deposition is 4-6 cm, the growth temperature is room temperature RT-300 ℃, and the thickness of the ZnS film is 20-60nm.
Example 2
Step 1: and depositing a ZnO film layer on the top end of the Mn core-shell nano rod array by using an electron beam evaporation method, wherein the purity of a ZnO target is 99.99%, the vacuum degree is better than 1.0x10 < -4 > Pa, the electron beam current is 8 mA during film coating, the anode voltage is 6 kV, the substrate temperature is RT-300 ℃, and the thickness of the ZnO film is 20-60nm. After the evaporation is finished, annealing the ZnO film layer sample for 0.5-1h at 300-500 ℃ under the vacuum condition of 7.5X10-5 Pa;
step 2: and depositing an Au film layer on the ZnO film layer by using an electron beam evaporation method, wherein the purity of an Au target is 99.999%, the vacuum degree is better than 1.0x10 < -4 > Pa, the electron beam current is 8 mA during film coating, the anode voltage is 6 kV, the substrate temperature is RT-100 ℃, and the thickness of the Au film is 6-30nm. After the evaporation is finished, annealing the Au film sample for 0.5-1h at 200-300 ℃ under the vacuum condition of 7.5X10-5 Pa;
step 3: depositing ZnS film layer on Au film layer by electron beam evaporation, wherein the purity of ZnS target is 99.99%, vacuum degree is better than 1.0X10-4 Pa, electron beam flow is 8 mA, anode voltage is 6 kV, substrate temperature is RT-300 ℃, and ZnS film thickness is 20-60nm. After the evaporation, the ZnS film sample is annealed for 0.5-1h at 300-500 ℃ under the vacuum condition of 7.5X10-5 Pa.
Example 3
Step 1: depositing a ZnO film layer on the top end of the Mn core-shell nanorod array by using a magnetron sputtering method, wherein the purity of a ZnO target is 99.99%, the background vacuum is 6 multiplied by 10 < -4 > Pa, 99.9% high-purity argon is adopted, the argon pressure is 0.1-0.2Pa, the argon flow is 20sccm, the sputtering power is 100W, the distance between the target and a substrate is 4-6 cm, the deposition temperature is RT-300 ℃, and the thickness of the ZnO film is 20-60nm;
step 2: depositing an Au film layer on the ZnO film layer by using a magnetron sputtering method, wherein the purity of an Au target is 99.999%, the background vacuum is 6 multiplied by 10 < -4 > Pa, 99.9% high-purity argon is adopted, the argon pressure is 0.1-0.2Pa, the argon flow is 20sccm, the sputtering power is 100W, the distance between the target and a substrate is 4-6 cm, the deposition temperature is RT-100 ℃, and the thickness of the Au film is 6-30nm;
step 3: depositing a ZnS film layer on the Au film layer by using a magnetron sputtering method, wherein the purity of a ZnS target is 99.99%, the background vacuum is 6 multiplied by 10 < -4 > Pa, 99.9% high-purity argon is adopted, the argon pressure is 0.1-0.2Pa, the argon flow is 20sccm, the sputtering power is 100W, the distance between the target and a substrate is 4-6 cm, the deposition temperature is RT-300 ℃, and the thickness of the ZnS film is 20-60nm.
In the actual production process, the preparation methods of the film layer and the ZnO nanorods adopted in the preparation process of the ZnS/ZnO/GaN core-shell nanorod array device and the transparent conductive film are not limited to the methods in the patent document, all the methods capable of preparing the film layer can be applied in the patent, the Au film layer in the transparent conductive film is not only limited to Au metal, but also can be replaced by other metals with good permeability and conductivity, ultraviolet excitation inspection is carried out after the preparation of the ZnS/Mn/ZnO/GaN core-shell nanorod array device is finished, if the preparation is not subjected to secondary test adjustment, the actual test and application of the transparent conductive film and the electrodes are increased if white light is emitted, so that the reject ratio of the produced products is reduced, and the production cost is reduced.
Claims (4)
1. The preparation method of the core-shell structure white light emitting device is characterized by comprising the following steps:
step one: cleaning a GaN substrate, taking a sapphire 0001 as the substrate, growing a 1 mu m-thick Mg-doped p-GaN film on an undoped GaN buffer layer, sequentially putting into acetone and ethanol solution, ultrasonically oscillating and cleaning for 10-30min, then washing with deionized water, drying with nitrogen, and enabling the luminescence peak position of the GaN substrate layer to be 430-450nm;
step two: depositing a ZnO film seed layer on the GaN substrate layer, wherein the method for depositing the ZnO film seed layer comprises the following steps: the thickness of the deposited ZnO is 30-50nm by a pulse laser deposition method, a magnetron sputtering method and an electron beam evaporation method;
step three: the ZnO nano rod is prepared on the ZnO film seed layer, and the method for preparing the ZnO nano rod comprises the following steps: hydrothermal synthesis, chemical water bath deposition and electrodeposition, wherein the luminescence peak positions of the ZnO nano rod are 375-387nm and 560-580nm;
step four: the ZnO nano rod is coated with a ZnS:Mn film shell layer, and the method for depositing the ZnS:Mn film shell layer comprises the following steps: pulse laser deposition, magnetron sputtering and electron beam evaporation, wherein the luminescence peak position of a ZnS: mn film shell layer is 580-610nm, a ZnO nano rod and a ZnS: mn film shell layer form a ZnO/ZnS: mn core-shell nano rod array, a ZnS: mn film shell layer, a ZnO nano rod, a ZnO film seed layer and a GaN substrate layer form a ZnS: mn/ZnO/GaN core-shell nano rod array device, blue light emitted by the GaN substrate layer can penetrate through an upper surface material under the excitation of ultraviolet light with 325nm wavelength, and the blue light and yellow-green light of the ZnO nano rod and orange-red light of the ZnS: mn film shell layer are overlapped to obtain white light, and the color coordinates are (0.31-0.35, 0.30-0.34) and then an electrode is added for practical production;
step five: depositing a transparent conductive film with the thickness of 100-120nm on the top end of the ZnO/ZnS-Mn core-shell nano-rod array, filling the gap of the ZnO/ZnS-Mn core-shell nano-rod array, and covering the top end of the ZnO/ZnS-Mn core-shell nano-rod array to enable the ZnO/ZnS-Mn core-shell nano-rod array to be connected with each other;
step six: preparing Pt/Ni50nm/30nm electrodes on the GaN substrate layer respectively, and preparing Pt/Ti50nm/30nm electrodes on the transparent conductive film coated with ZnO/ZnS: mn core-shell nanorod array surface;
step seven: the ZnS: mn/ZnO/GaN core-shell nanorod array is excited by forward voltage to obtain white light emission with stronger visible light region, the wavelength range of the obtained white light emission spectrum is 350-800nm, and the color coordinates are (0.335-0.3393, 0.3334-0.3366).
2. The method for manufacturing a white light emitting device with a core-shell structure according to claim 1, wherein the transparent conductive film is an ITO transparent conductive film.
3. The method for preparing the core-shell structure white light emitting device according to claim 1, wherein the doping concentration of Mn2+ in the ZnS: mn film shell is 1% -3%.
4. The method for manufacturing a white light emitting device with a core-shell structure according to claim 1, wherein the optimized doping concentration of mn2+ in the ZnS: mn thin film shell layer is 1%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710706337.8A CN107316927B (en) | 2017-08-17 | 2017-08-17 | Core-shell structure white light emitting device and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710706337.8A CN107316927B (en) | 2017-08-17 | 2017-08-17 | Core-shell structure white light emitting device and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107316927A CN107316927A (en) | 2017-11-03 |
| CN107316927B true CN107316927B (en) | 2023-11-07 |
Family
ID=60176004
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710706337.8A Active CN107316927B (en) | 2017-08-17 | 2017-08-17 | Core-shell structure white light emitting device and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107316927B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108754442A (en) * | 2018-06-04 | 2018-11-06 | 中建材蚌埠玻璃工业设计研究院有限公司 | A kind of preparation method of ZnS clading ZnO nanos nucleocapsid laminated film |
| CN110190162A (en) * | 2019-06-04 | 2019-08-30 | 深圳扑浪创新科技有限公司 | A kind of epitaxial structure of LED chip and preparation method thereof |
| CN111252805A (en) * | 2020-03-12 | 2020-06-09 | 广州特种承压设备检测研究院 | Preparation method of novel zinc oxide material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1813357A (en) * | 2003-06-26 | 2006-08-02 | 学校法人浦项工科大学校 | P-n heterojunction structure of zinc oxide-based nanorod and semiconductor thin film, preparation thereof, and nano-device comprising same |
| CN101378091A (en) * | 2008-09-19 | 2009-03-04 | 武汉大学 | n-ZnO nanometer line/p-NiO alloplasm heterogeneous pn junction diode and preparation method thereof |
| CN103227230A (en) * | 2013-04-10 | 2013-07-31 | 中国科学院安徽光学精密机械研究所 | Lateral growth ZnMgO nanowire solar-blind region ultraviolet detector and fabrication method thereof |
| CN104051589A (en) * | 2014-06-24 | 2014-09-17 | 东南大学 | Transverse zinc oxide nanorod array light emitting diode |
| CN104638066A (en) * | 2015-02-09 | 2015-05-20 | 浙江大学 | ZnO/ZnS/FeS 2-core-shell structure array film and preparing method |
| CN207250548U (en) * | 2017-08-17 | 2018-04-17 | 滨州学院 | A kind of core shell structure turns white optical device |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040059300A (en) * | 2002-12-28 | 2004-07-05 | 학교법인 포항공과대학교 | Nanostructure comprising magnetic material and nanomaterial and method for manufacturing thereof |
| US8330173B2 (en) * | 2005-06-25 | 2012-12-11 | Seoul Opto Device Co., Ltd. | Nanostructure having a nitride-based quantum well and light emitting diode employing the same |
-
2017
- 2017-08-17 CN CN201710706337.8A patent/CN107316927B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1813357A (en) * | 2003-06-26 | 2006-08-02 | 学校法人浦项工科大学校 | P-n heterojunction structure of zinc oxide-based nanorod and semiconductor thin film, preparation thereof, and nano-device comprising same |
| CN101378091A (en) * | 2008-09-19 | 2009-03-04 | 武汉大学 | n-ZnO nanometer line/p-NiO alloplasm heterogeneous pn junction diode and preparation method thereof |
| CN103227230A (en) * | 2013-04-10 | 2013-07-31 | 中国科学院安徽光学精密机械研究所 | Lateral growth ZnMgO nanowire solar-blind region ultraviolet detector and fabrication method thereof |
| CN104051589A (en) * | 2014-06-24 | 2014-09-17 | 东南大学 | Transverse zinc oxide nanorod array light emitting diode |
| CN104638066A (en) * | 2015-02-09 | 2015-05-20 | 浙江大学 | ZnO/ZnS/FeS 2-core-shell structure array film and preparing method |
| CN207250548U (en) * | 2017-08-17 | 2018-04-17 | 滨州学院 | A kind of core shell structure turns white optical device |
Non-Patent Citations (1)
| Title |
|---|
| p-GaN衬底ZnO/ZnS:Mn核壳纳米棒阵列的制备及其发光性质的研究;胡海峰;CNKI硕士电子期刊;1-24 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107316927A (en) | 2017-11-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107316927B (en) | Core-shell structure white light emitting device and preparation method thereof | |
| TW467874B (en) | Semiconductor light-emitting device, method of manufacturing transparent conductor film and method of manufacturing compound semiconductor light-emitting device | |
| CN102169930B (en) | Method for coarsening surface of light-emitting diode (LED) with the aid of metal nanoparticles | |
| CN105185908A (en) | Solution-processed organic-inorganic planar heterojunction light emitting diode and manufacturing method thereof | |
| CN103840053A (en) | Surface-plasma-enhanced quantum dot light-emitting diode device and manufacturing method thereof | |
| CN105098004B (en) | The growing method and epitaxial wafer of a kind of LED epitaxial slice | |
| CN101964386A (en) | Method for manufacturing surface-coarsened light emitting diode | |
| CN104051589B (en) | Transverse zinc oxide nanorod array light emitting diode | |
| CN106601884B (en) | Zno-based nano rod/compound UV LED of Quantum Well and preparation method thereof | |
| Guan et al. | Colour optimization of phosphor-converted flexible nitride nanowire white light emitting diodes | |
| CN207250548U (en) | A kind of core shell structure turns white optical device | |
| CN102637783A (en) | White-light emitting diode with vertical structure and manufacturing method thereof | |
| CN103956416A (en) | ZnO-based white light LED and preparing method thereof | |
| Cheng et al. | Boosted electroluminescence of perovskite light-emitting diodes by pinhole passivation with insulating polymer | |
| Chawla et al. | Enhancement of luminescence in ZnMgO thin‐film nanophosphors and application for white light generation | |
| KR101288367B1 (en) | White light emitting diode and manufacturing method thereof | |
| CN110880557A (en) | Alternating current driven non-toxic QLED | |
| CN207338418U (en) | A kind of light emitting diode (LED) chip with vertical structure based on photonic crystal | |
| CN107731971A (en) | A kind of light emitting diode (LED) chip with vertical structure based on photonic crystal and preparation method thereof | |
| KR20120064866A (en) | Ultra violet light emitter by using electric field emitter and fabrication method thereby | |
| CN102956774A (en) | Method for fabricating nanoscale column array GaN-based normal-structured light emitting diode | |
| CN103022288A (en) | Light emitting diode and manufacturing method thereof | |
| CN108511583B (en) | A kind of white light LEDs and preparation method thereof | |
| CN202009030U (en) | White light-emitting diode (LED) with vertical structure | |
| CN102522469B (en) | ZnO substrate epitaxy structure, manufacture method thereof and ZnO substrate chip structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |